ZnO films were implanted with phosphorus in the range from 5×10 12 to 5×10 15 cm -2 . Effect of phosphorus concentration on structural characteristics and photoelectric behavior of phosphorus-implanted ZnO films under different atmosphere and annealing treatment was investigated. It has been demonstrated that below solubility (1.5×10 18 ions/cm 3 ), the defect formation will be dominated by annealing atmosphere and more defects can be formed in oxygen ambient than in nitrogen atmosphere as revealed from PL spectra. However, excess phosphorus doping, above solubility (1.5×10 18 ions/cm 3 ), will induce the formation of the phosphide compounds in ZnO films and seriously deteriorate the crystallinity and optical property of the films. However, a high-resistive but not p-type ZnO film is obtained by phosphorus doping.